KR102606523B1 - Activated Spray-Dried Ziegler-Natta Catalyst System - Google Patents

Abstract

A titanium-based Ziegler-Natta catalyst, a carrier material, and an activator mixture comprising an effective amount of an activator mixture comprising triethylaluminum and diethylaluminum chloride to produce a substantially uniform comonomer composition distribution. Activated, titanium-based, spray-dried Ziegler-Natta catalyst system. Also, polyolefin; Methods of making and using them; and articles containing them.

Description

Activated Spray-Dried Ziegler-Natta Catalyst System

It relates to titanium-based Ziegler-Natta catalysts, polyolefins, methods of making and using them, and articles containing them.

Ziegler-Natta (precursor) catalysts can be based on titanium or vanadium. A typical Ziegler-Natta procatalyst contains a complex of TiCl ₃ and MgCl ₂ . MgCl ₂ is a segmented solid that has a high surface area and also acts as a support material.

A typical Ziegler-Natta procatalyst system includes a Ziegler-Natta procatalyst and at least one additional component other than a reducing agent or activator. Examples of at least one additional ingredient are organic modifiers and carrier substances.

A typical Ziegler-Natta catalyst system includes a Ziegler-Natta catalyst that sequentially comprises the reaction products of chemical reduction and chemical activation of the Ziegler-Natta procatalyst system. Accordingly, the Ziegler-Natta catalyst system comprises contacting the Ziegler-Natta procatalyst system with a reducing agent effective to chemically reduce the Ziegler-Natta procatalyst system to produce a chemical reduction product, and combining the chemical reduction product with an activator. By increasing its catalytic activity and preparing a Ziegler-Natta catalyst system by contacting with Nichapat Senso, et al.; Molecules , 2010, 15, 9323-9339]; and WO 2006/138036 A1 and its clade member EP1891125; WO 2010/125018 A1; and WO 2017/151592 A1.

In a Ziegler-Natta catalyst system, the Ziegler-Natta catalyst can enhance the rate of polymerization of olefin monomer(s). Organic modifiers may attenuate the catalytic activity or selectivity of a Ziegler-Natta catalyst, such as a function of reaction temperature, or may alter the composition or reactivity of the activator. The carrier material typically defines the size and shape of the Ziegler-Natta catalyst and controls access of monomers to the catalyst. The function of the carrier material can vary from catalyst system to catalyst system depending on how the catalyst system is constructed, which in turn largely depends on how the catalyst system is manufactured and the composition and characteristics of the carrier material.

The carrier material is a segmented solid and has a different composition from that of the titanium halide and the support material. The carrier material may be alumina, clay or silica. The carrier material may be porous, such as mesoporous, and thus may define an external surface (outside the pores) and an internal surface (inside the pores). Ziegler-Natta catalyst systems comprising Ziegler-Natta catalysts and carrier materials can be classified according to characteristics such as the size, shape and location of the Ziegler-Natta catalyst within the system. In other words, these characteristics can be adjusted depending on the composition of the carrier material of the Ziegler-Natta catalyst system and the preparation method.

In supported Ziegler-Natta catalyst systems, the carrier material can be mesoporous spheres of amorphous untreated silica, where the inner and outer surfaces are hydrophilic. Supported Ziegler-Natta catalyst systems generally include suspending porous silica in a tetrahydrofuran solution of titanium chloride and magnesium chloride to form a mixture, and then concentrating the mixture under vacuum to form a supported Ziegler-Natta procatalyst. It can be prepared by a concentration method comprising providing a system, and this procatalyst system can be subsequently reduced and activated. The concentration method causes the Ziegler-Natta procatalyst to precipitate within the pores of porous silica, and after chemical reduction and activation steps, the pores are believed to contain most or all of the Ziegler-Natta catalyst. Therefore, without wishing to be bound by theory, it is generally believed that the pores of the porous silica define the size and shape of the Ziegler-Natta catalyst in supported Ziegler-Natta catalyst systems and control monomer access to the catalyst. During polymerization, ethylene and/or alpha-olefins may enter the pores of the porous silica and contact the Ziegler-Natta catalyst therein, within which the growth of the polymer may be constrained by the mesopore diameter and pore volume. Commercial supported Ziegler-Natta catalyst systems include UCAT™ A from Univation Technologies, LLC.

In spray-dried Ziegler-Natta catalyst systems, the carrier material can be hydrophobically pretreated fumed silica, wherein the inner and outer surfaces are hydrophobic. The spray-dried Ziegler-Natta catalyst system consists of suspending hydrophobically pretreated silica (pretreated with a hydrophobizing agent) in a tetrahydrofuran solution of the Ziegler-Natta procatalyst to form a mixture, and spray-drying the mixture. It can be prepared by a spray-drying method comprising providing a spray-dried Ziegler-Natta procatalyst system, which procatalyst system can be subsequently reduced and activated. It is believed that the spray-drying process results in hydrophobic pores containing either relatively small amounts of Ziegler-Natta catalyst or no Ziegler-Natta catalyst, with the Ziegler-Natta catalyst instead largely remaining on the external surface. Therefore, without wishing to be bound by theory, it is believed that the external surface generally defines the size and shape of the Ziegler-Natta catalyst in spray-dried Ziegler-Natta catalyst systems and controls monomer access to the catalyst. During polymerization, ethylene and/or alpha-olefin can be contacted with a Ziegler-Natta catalyst on the outer surface of the silica, on which the resulting polymer can grow largely unconstrained by pore dimensions. Commercial spray-dried Ziegler-Natta catalyst systems include UCAT™ J from Univation Technologies, LLC.

Therefore, knowledge of supported Ziegler-Natta (pro)catalyst systems does not necessarily predict or apply to spray-dried Ziegler-Natta (pro)catalyst systems, and vice versa.

The inventors have disclosed a titanium-based Ziegler-Natta catalyst, a carrier material, and an activator mixture comprising effective amounts of triethylaluminum (TEAl) and diethylaluminum chloride (DEAC); or activated, titanium-based, spray-dried Ziegler-Natta catalyst systems comprising their activation reaction products. The catalyst system of the present invention can be used to enhance the polymerization reaction rate of chemical processes for producing polyolefin compositions. In this method, the effective amount is sufficient to obtain a substantially uniform (substantially flat (gently sloping) plot) comonomer composition distribution of the ethylene/alpha-olefin copolymer composition prepared with the activator mixture. It can be positive. When the activator mixture is used in such an effective amount, this unexpectedly results in the catalyst system of the present invention copolymerizing ethylene and an alpha-olefin comonomer, such that the activator of the comparative catalyst system consists of triethylaluminum (TEAl) and diethyl An ethylene/alpha-olefin copolymer having a substantially more uniform comonomer composition distribution than a comparative ethylene/alpha-olefin copolymer produced with a comparative catalyst system identical to the catalyst system of the invention except for the absence of aluminum chloride (DEAC). It makes it possible to produce a composite composition. The substantially uniform comonomer composition distribution of the ethylene/alpha-olefin copolymer compositions of the present invention will be advantageous for the production of films with improved mechanical properties in a regime recognized by the inventors. Alternatively or additionally, the effective amount may have a higher fluidized bulk density (FBD) and/or a higher settled bulk density (SBD) compared to the comparative ethylene/alpha-olefin copolymer composition prepared with the comparative catalyst system. The amount of activator mixture may be sufficient to produce the ethylene/alpha-olefin copolymer composition of the invention with a settled bulk density) and/or a higher dart impact (film formation). In some embodiments, the inventive FBD and/or inventive SBD of the inventive ethylene/alpha-olefin copolymer composition and/or the inventive dart impact film of the inventive ethylene/alpha-olefin copolymer composition is independently at least 5%, alternatively at least 10% less than the dart impact of each of the FBD and/or SBD of the comparative ethylene/alpha-olefin copolymer composition and/or the film of the comparative ethylene/alpha-olefin copolymer composition, respectively. ; and in some embodiments as much as 20% or higher. The inventors also provide a method for making the catalyst system of the invention, a method for polymerizing the olefin (co)monomer(s), a polyolefin prepared by the method, and an article of manufacture containing or made from the polyolefin. to provide. Polymerization can be carried out in gas phase or liquid phase.

Figure 1 shows the comonomer content weight percent (% by weight) of the ethylene/alpha-olefin copolymer composition on the y-axis for each of Examples (A) and (B) and Comparative Example (A) of the present invention. Contains a line plot of change versus change in LogM (by GPC) of the ethylene/alpha-olefin copolymer composition on the x-axis.

The background, disclosure, and abstract are hereby incorporated by reference.

Specific embodiments of the invention are described below in numbered form for ease of cross-reference. Additional embodiments are described elsewhere herein.

Embodiment 1. Activated spray-dried Ziegler-Natta catalyst system comprising (A*) an activated Ziegler-Natta catalyst comprising an activated complex of TiCl ₃ and MgCl ₂ , (B) hydrophobic pretreated fumed silica (substantially non-free) porous, alternatively completely non-porous), and an effective amount of (C) an activator mixture of triethylaluminum (TEAl) and diethylaluminum chloride (DEAC) in a TEAl/DEAC weight/weight ratio of 20:80 to 80:20. ; or an activated spray-dried Ziegler-Natta catalyst system comprising their activation reaction products. The effective amount is a comparative activated spray that is activated with TEAI alone or DEAC alone and prepared with the same melt index value (I ₂ ) as determined by the melt index test method and the same density as determined by the density test method described hereinafter. -Comparative polyethylene compositions made with dried Ziegler-Natta catalyst systems, such as polyethylene compositions having a higher flowing bulk density and/or a higher settled bulk density compared to comparative ethylene/alpha-olefin copolymer compositions, such as ethylene/alpha- The amount is sufficient to obtain a substantially uniform comonomer composition distribution of the ethylene/alpha-olefin copolymer composition for making and preparing the olefin copolymer composition. The substantially uniform (narrower) comonomer composition distribution (CCD) of the ethylene/alpha-olefin copolymer compositions of the present invention may be a significant reason for the better physical properties of the compositions.

Aspect 2. The method of Embodiment 1, wherein (C) the effective amount of the activator mixture is 25:75 to 75:25, alternatively 30.0:70.0 to 70.0:30.0, alternatively 35:65 to 65:35, alternatively Activated spray-drying, with a TEAl/DEAC weight/weight ratio of 40.0:60.0 to 60.0:40.0, alternatively 45:55 to 55:45, alternatively 47:53 to 53:47, alternatively 50:50. Ziegler-Natta catalyst system.

Aspect 3. A method of preparing an activated spray-dried Ziegler-Natta catalyst system, comprising: (A ^red ) a chemically-reduced Ziegler-Natta catalyst comprising a complex of TiCl ₃ and MgCl ₂ and (B) Preparing an activated spray-dried Ziegler-Natta catalyst system by contacting a chemically-reduced spray-dried Ziegler-Natta catalyst system comprising hydrophobic pretreated fumed silica with an effective amount of (C) activator mixture. Method, including. The activator may include one or more alkylaluminum compounds, such as a combination of diethylaluminum chloride and triethylaluminum. The activation reaction is carried out under an inert gas atmosphere and in a saturated and/or aromatic hydrocarbon solvent, such as an alkane; mixtures of two or more alkanes; mineral oil; Alkyl-substituted benzene, such as toluene, ethylbenzene or xylene; Or it may proceed in a mixture of any two or more of these. The activation reaction may use the reaction mixture prepared in the previous embodiment of the reduction reaction and may proceed in the same reactor as the reduction reaction. The resulting activated spray-dried Ziegler-Natta catalyst system can then be fed into a polymerization reactor, such as a polymerization reactor used under the method of making polyethylene compositions. Alternatively, the activation reaction may proceed in a polymerization reactor, wherein a first feed of the chemically-reduced spray-dried Ziegler-Natta catalyst system is introduced into the polymerization reactor via a first feed line; Separately, this may be achieved by producing an activated spray-dried Ziegler-Natta catalyst system in situ in the polymerization reactor by introducing a second feed of activator into the polymerization reactor through a second feed line, The first feed line and the second feed line are different and introduce their respective feeds at different feed points to the polymerization reactor. Alternatively, the activation reaction may be accomplished by introducing a first feed of the chemically-reduced spray-dried Ziegler-Natta catalyst system and a second feed of activator into a co-feed line, any downstream of which enters the polymerization reactor. This can initiate the production of an activated spray-dried Ziegler-Natta catalyst system in situ in a co-feed line, followed by the chemically-reduced spray-dried catalyst system prepared in the co-feed line. Spray-dried Ziegler-Natta catalyst system activated in the polymerization reactor by co-feeding the resulting mixture of Ziegler-Natta catalyst system and activator and any such activated catalyst system into the polymerization reactor from the co-feed line. This can be achieved by manufacturing. Activated spray-dried Ziegler-Natta catalyst systems can be dried by removing the saturated and/or aromatic hydrocarbon solvent from the system. Without wishing to be bound by theory, the present inventors believe that the outer surface of hydrophobic pretreated fumed silica largely defines the composition of the (A*) activated Ziegler-Natta catalyst in activated spray-dried Ziegler-Natta catalyst systems. I think it is The activated spray-dried Ziegler-Natta catalyst system of Aspect 1 or 2, which may be the product of the process of Aspect 3. The term “spray-dried” refers to the construction of an activated Ziegler-Natta catalyst in an (A*) activated spray-dried Ziegler-Natta catalyst system in Embodiments 1 to 3, as described hereinafter. It is used in the conventional sense recognized in the art, which derives from the effect of the prior stage of. (A*) activated Ziegler-Natta catalysts have a catalytic activity and/or polymer productivity per unit catalyst weight that is at least 10 times higher than (A ^red ) chemically-reduced Ziegler-Natta catalysts.

Aspect 4. A method of making a polyethylene composition comprising ethylene (monomer) and optionally 0, 1 or more (C ₃ -C ₂₀ )alpha-olefins (comonomer(s)) of Aspect 1 or 2. By contacting with an activated spray-dried Ziegler-Natta catalyst system, a polyethylene homopolymer or ethylene/(C ₃ -C ₂₀ )alpha-olefin copolymer composition, respectively, and an activated spray-dried Ziegler-Natta catalyst system, or both. A method comprising providing a polyethylene composition comprising a by-product. Polyethylene homopolymers contain component units derived from ethylene. Ethylene/(C ₃ -C ₂₀ )alpha-olefin copolymers have monomeric component units derived from ethylene and comonomeric components derived from one or more (C ₃ -C ₂₀ )alpha-olefin comonomer(s). Each contains a unit. (C ₃ -C ₂₀ )alpha-olefin-derived comonomeric building blocks include 1-butene; alternatively 1-hexene; alternatively 1-octene; Alternatively it may be derived from a combination of any two of these.

Embodiment 5. The method of Embodiment 4, wherein gas phase polymerization is carried out in one, two or more gas phase polymerization reactors under (co)polymerization conditions in the presence of molecular hydrogen gas (H ₂ ) and, optionally, an induction condensation agent (ICA), comprising preparing a polyethylene composition; The (co)polymerization conditions include a reaction temperature of 80 degrees Celsius (°C) to 110 degrees Celsius (°C); a molar ratio of molecular hydrogen gas to ethylene (H ₂ /C ₂ molar ratio) of 0.001 to 0.050; and a molar ratio of comonomer to ethylene (comonomer/C ₂ molar ratio) of 0.005 to 0.10.

Aspect 6. The method of Aspect 4 or 5, wherein ethylene and one or more (C ₃ -C ₂₀ )alpha-olefins (comonomer(s)) are copolymerized to produce an ethylene/(C ₃ -C ₂₀ )alpha-olefin copolymer composition. A method comprising the steps of providing.

Aspect 7. A polyethylene composition prepared by the method of Aspect 4, 5 or 6.

Aspect 8. An article of manufacture comprising a shaped form of the polyethylene composition of Aspect 7. The article of manufacture may be selected from coatings, films, sheets, extruded articles, and injection molded articles. Articles of manufacture include coatings (e.g. coating layers of coated articles), pipes, films (e.g. hollow films), agricultural films, food packaging, garment bags, shopping bags, heavy sacks. -duty sack), industrial sheets, pallets and shrink wrap, bags, buckets, freezer containers, lids and toys.

_Embodiment 9. The method of Embodiment 3, further comprising the preliminary step of preparing a chemically-reduced spray-dried Ziegler-Natta catalyst system, wherein the method comprises: providing a chemically-reduced spray-dried Ziegler-Natta catalyst system by contacting the complex of MgCl ₂ with a reducing agent effective to chemically reduce the complex; The spray-dried Ziegler-Natta procatalyst system consists essentially of a complex of (A ⁺ ) TiCl ₃ and MgCl ₂ and (B) hydrophobically pretreated fumed silica, and optionally tetrahydrofuran. A method comprising the product of a dry-spray slurry. In some embodiments, the titanium composite is made from TiCl4 and Mg metal (MgO). In some embodiments, the titanium composite is prepared from TiCl ₄ and Mg metal, and the slurry of components (A ⁺ ) and (B) is heated by heating the TiCl ₄ and Mg metal in anhydrous tetrahydrofuran at a first temperature for a first period of time. Thus, providing a first solution of the complex of TiCl ₃ and MgCl ₂ in anhydrous tetrahydrofuran, adding finely divided solid MgCl ₂ to the first solution to obtain MgCl 3 in the solution of the complex of TiCl ₃ and anhydrous tetrahydrofuran. providing a suspension of ₂ , wherein the finely divided solid MgCl ₂ is dissolved to form a second solution of the complex of TiCl ₃ and MgCl ₂ and added MgCl ₂ in anhydrous tetrahydrofuran for a second period of time at a second temperature; heating until provided, and adding (B) hydrophobic pretreated fumed silica at a third temperature to the second solution to provide a slurry of components (A ⁺ ) and (B). Manufactured through 1 process. In another aspect, the titanium composite is made from TiCl ₃ .AA and MgCl ₂ . “TiCl ₃ .AA” means a mixture of TiCl ₃ /AlCl ₃ in a 3:1 molar ratio, which mixture can be obtained from commercial suppliers or is composed of 3 molar equivalents of TiCl ₄ and 1 molar equivalent acting as reducing agent. It can be manufactured by the reaction of aluminum (Al) metal (Al ⁰ ). In another embodiment, the titanium composite is prepared from TiCl ₃ .AA and MgCl ₂ , wherein the slurry of components (A+) and (B) comprises drying the finely divided solid MgCl ₂ in anhydrous tetrahydrofuran for a second period at a first temperature. providing a third solution of MgCl ₂ in anhydrous _{tetrahydrofuran} by heating in providing a fourth solution of a complex of TiCl ₃ .AA and MgCl ₂ and additional MgCl ₂ , and adding (B) hydrophobic pretreated fumed silica to the fourth solution at a third temperature to obtain component (A) ⁺ is prepared by a second process comprising providing a slurry of ) and (B). The slurry produced by the first or second process can be mixed for a third period and then spray-dried to provide a modified spray-dried Ziegler-Natta procatalyst system. Suitable spray-drying conditions are described later in the examples. The first temperature and the second temperature are independently 30 degrees Celsius (°C) to the boiling point of component (C), alternatively 50°C to 65°C, alternatively 58°C to 62°C, alternatively 60°C. You can. The first period may be 10 to 120 minutes, alternatively 45 to 90 minutes, alternatively 50 to 70 minutes, alternatively 60 minutes. The second period may be 1 to 48 hours, alternatively 3 to 30 hours, alternatively 4 to 12 hours, alternatively 5 hours. The third temperature may be 30°C to 55°C, alternatively 35°C to 50°C, alternatively 35°C to 45°C, alternatively 40°C to 45°C. The third period may be 5 to 60 minutes, alternatively 10 to 45 minutes, alternatively 20 to 40 minutes, alternatively 30 minutes. In a first process, measured amounts of TiCl ₄ and Mg metal may be added to measured amounts of anhydrous tetrahydrofuran in a vessel. For enhanced performance of the activated Ziegler-Natta catalyst (see below) comprising a complex of (A*) TiCl ₃ and MgCl ₂ ultimately prepared, in a first process, the addition of TiCl ₄ and Mg metal and the first Formation of the first solution by subsequent heating at temperature is carried out before the finely divided solid MgCl ₂ is added to anhydrous tetrahydrofuran. In a variation of the first process, if finely divided solid MgCl ₂ is added to the anhydrous tetrahydrofuran modifier before the TiCl ₄ and Mg metal are added to the anhydrous tetrahydrofuran, ultimately the produced (A*) TiCl ₃ and MgCl The performance of activated Ziegler-Natta catalysts (see below) containing the complex of ₂ may not be enhanced. The carrier material of the activated spray-dried Ziegler-Natta catalyst system consists essentially of, or alternatively consists of (B) hydrophobic pretreated fumed silica, wherein the carrier material has 0 to 5 weight percent (% by weight) , alternatively 0 to 0.9% by weight, alternatively 0 to 0.09% by weight, alternatively 0% by weight of porous silica. Without wishing to be bound by theory, the inventors believe that the outer surface of the hydrophobic pretreated fumed silica largely defines the configuration of the (A) Ziegler-Natta procatalyst in the spray-dried Ziegler-Natta procatalyst system. The reducing agent may include trihexyl aluminum, diethylaluminum chloride, or typically a combination of trihexyl aluminum and diethylaluminum chloride. The reduction reaction is carried out under an inert gas atmosphere and in a saturated and/or aromatic hydrocarbon solvent, such as an alkane; mixtures of two or more alkanes; mineral oil; Alkyl-substituted benzene, such as toluene, ethylbenzene or xylene; Or it may proceed in a mixture of any two or more of these. The saturated and/or aromatic hydrocarbon solvent used in the activation reaction may be the same or different from the saturated and/or aromatic hydrocarbon solvent used in the reduction reaction. Chemically-reduced spray-dried Ziegler-Natta catalyst systems can be dried by removing the saturated and/or aromatic hydrocarbon solvent from the system. Without wishing to be bound by theory, the present inventors have demonstrated the composition of a (A ^red ) chemically-reduced Ziegler-Natta catalyst in a spray-dried Ziegler-Natta catalyst system in which the outer surface of hydrophobic pretreated fumed silica is activated. Generally, it is considered limited. The term “spray-dried” is used in these embodiments in its conventional art-recognized sense that the construction of activated spray-dried Ziegler-Natta catalyst systems derives from the effects of the prior step of spray-drying.

Embodiment 10. The method of Embodiment 9, further comprising a preliminary step of preparing a spray-dried Ziegler-Natta procatalyst system, wherein the method comprises (B) hydrophobic pretreated fumed silica and (A ⁺ ) Ziegler-Natta procatalyst. and optionally spray-drying the mixture of solutions of tetrahydrofuran to provide a spray-dried Ziegler-Natta procatalyst system. The spray-dried Ziegler-Natta procatalyst system of Embodiments 8 or 9 has not yet been contacted with a reducing agent effective to chemically reduce the complex of TiCl ₃ and MgCl ₂ . The carrier material of the spray-dried Ziegler-Natta procatalyst system consists essentially of, or alternatively consists of (B) hydrophobic pretreated fumed silica, wherein the carrier material is present in an amount of 0 to 5 weight percent (% by weight), alternatively 0 to 0.9% by weight, alternatively 0 to 0.09% by weight, alternatively 0% by weight of porous silica. Without wishing to be bound by theory, the inventors believe that the outer surface of the hydrophobic pretreated fumed silica largely defines the configuration of the (A) Ziegler-Natta procatalyst in the spray-dried Ziegler-Natta procatalyst system.

Aspect 11. The method of Aspect 9 or 10, further described by any one of restrictions (i) to (i): (i) the titanium chloride is TiCl ₃ ; (ii) titanium chloride is limited to TiCl ₄ ; (iii) titanium chloride is limited to a combination of TiCl ₃ and TiCl ₄ ; (iv) (B) Hydrophobic pretreated fumed silica is the product of pretreatment of untreated fumed silica with a silicon-based hydrophobizing agent; (v) Hydrophobic pretreated fumed silica can be prepared by mixing untreated fumed silica with trimethylsilyl chloride, dimethyldichlorosilane, polydimethylsiloxane fluid, hexamethyldisilazane, octyltrialkoxysilane (e.g., octyltrimethoxysilane). , and a combination of any two or more of these; (vi) both (ii) and (v). An example of hydrophobically treated fumed silica is CAB-O-SIL hydrophobic fumed silica, available from Cabot Corporation, Alpharetta, GA.

Spray-dried Ziegler-Natta procatalyst system; chemically-reduced, spray-dried Ziegler-Natta procatalyst system; and spray-dried Ziegler-Natta catalyst systems can be collectively referred to as spray-dried Ziegler-Natta (pro)catalyst systems. Spray-dried Ziegler-Natta procatalyst system; chemically-reduced, spray-dried Ziegler-Natta procatalyst system; and the spray-dried Ziegler-Natta catalyst system may independently be characterized by any one of the limits (i) to (x): (i) 2.0, based on the total weight of the system ad rem. Mg atomic loading of from 10.0 weight percent (%), alternatively from 6.0 to 8.5%, alternatively from 6.5 to 8.0% by weight; (ii) 0.82 to 4.11 millimoles Mg atoms per gram of suitable system (mmol/g), alternatively 2.0 to 4.0 mmol/g, alternatively 2.47 to 3.50 mmol/g, alternatively 2.67 to 3.29 mmol/g. Mg atomic concentration; (iii) a Ti atom loading of 0.5 to 5.0 wt.%, alternatively 1.0 to 4.0 wt.%, alternatively 1.5 to 3.5 wt.%, based on the total weight of the appropriate system; (iv) suitable systems 0.10 to 1.04 millimoles per gram of Ti (mmol/g), alternatively 0.21 to 0.84 mmol/g, alternatively 0.25 to 0.80 mmol/g, alternatively 0.31 to 0.73 mmol/g of Ti. atomic concentration; (v) Mg atom-to-Ti atom molar ratio of 0.79 to 39.4, alternatively 2.95 to 16.7, alternatively 3.0 to 15, alternatively 3.66 to 10.5; (vi) a loading of tetrahydrofuran/ethanol modifier of 15 to 45 weight percent, alternatively 18 to 39 weight percent, alternatively 20.0 to 35.0 weight percent; (vii) both (i) and (ii); (viii) both (i) and (iii); (ix) both (i) and (iv); (x) both (i) and (v); (xi) both (i) and (vi); (xii) both (ii) and (iii); (xiii) both (ii) and (iv); (xiv) both (ii) and (v); (xv) both (ii) and (vi); (xvi) both (iii) and (iv); (xvii) both (iii) and (v); (xviii) both (iii) and (vi); (xix) both (iv) and (v); (xx) both (iv) and (vi); (xxi) both (v) and (vi); (xxii) any one of (vii) and (viii) to (xxi); (xxiii) both (viii) and any one of (ix) to (xxi); (xxiv) both (ix) and any one of (x) to (xxi); (xxv) both (x) and any one of (xi) to (xxi); (xxvi) any one of (xi) and (xii) to (xxi); (xxvii) any one of (xii) and (xiii) to (xxi); (xxviii) any one of (xiii) and (xiv) to (xxi); (xxix) any one of (xiv) and (xv) to (xxi); (xxx) any one of (xv) and (xvi) through (xxi); (xxxi) any one of (xvi) and (xvii) through (xxi); (xxxii) both (xvii) and any one of (xviii) to (xxi); (xxxiii) both (xviii) and any one of (xix) to (xxi); (xxxiv) both (xix) and any one of (xx) to (xxi); (xxxv) Both (xx) and (xxi).

The catalyst system of the present invention has an improved composition and, optionally, an improved configuration. Without wishing to be bound by theory, the improved compositions, and optionally the improved constructs, may be the reason for the ethylene/alpha-olefin copolymer compositions of the invention having a substantially uniform (flattened diagram) comonomer composition distribution. It is believed that there is. It is believed that the ethylene/alpha-olefin copolymer compositions of the present invention may have at least one additional improved property. In some embodiments, an inventive activated spray-dried Ziegler-Natta catalyst system prepared according to the inventive polymerization process (e.g., hereinafter referred to as an inventive activated spray-dried Ziegler-Natta catalyst system of Inventive Example 1) dried Ziegler-Natta catalyst systems) and inventive ethylene/alpha-olefin copolymer compositions (e.g., inventive ethylene/1-butene copolymer compositions of inventive Example (A) described later) Silver, a corresponding comparative ethylene/alpha-olefin copolymer composition (e.g. For example, the comparative ethylene/1-butene copolymer of Comparative Example (A) described hereinafter) is characterized by at least one of the following normalized properties: (i) a normalized ratio of at least 110, alternatively at least 111; Elmendorf MD Tear; (ii) a normalized Elmendorf CD tear of at least 120, alternatively at least 121; (iii) a normalized 2% MD Secant Modulus of at least 104; (iv) a normalized 2% CD secant coefficient of at least 110, alternatively at least 111; (v) Normalized Dart Impact of at least 105; (vi) a normalized gloss (45°) of at least 110, alternatively at least 120, alternatively at least 130, alternatively at least 135; (vii) Normalized Optical Haze of at most 90, alternatively at most 80, alternatively at most 75; (viii) a normalized transparency of at least 110, alternatively at least 115; (ix) at least two of (i) to (viii); and (x) (i) to (viii) respectively. The unexpected improvements described above are later illustrated in Table 3.

All else being equal, an activated spray-dried Ziegler-Natta catalyst system of the present invention (catalyst system of the present invention) may be used in the polymerization process of the present invention, consisting of triethylaluminum (i.e., diethylaluminum chloride). Polyethylene compositions, such as ethylene/alpha-, unexpectedly have higher flowing bulk densities and/or higher settled bulk densities than comparative compositions made with comparative activated spray-dried Ziegler-Natta catalyst systems that were activated with an activator (lacking). An olefin copolymer composition can be prepared. A higher fluidized bulk density (FBD) is beneficial to the performance of the polymerization reaction in a fluidized bed gas phase polymerization (FB-GPP) reactor arranged with a distributor plate to suppress the loss of fines from the fluidized bed because less This is because polymer particles can become trapped within the distributor plate and clog it. Higher FBD also allows the polymerization reaction to use higher resin bed weights, providing higher space time yield (STY, or flow bulk density per polymer residence time) and production rate. Higher settled bulk densities (SBD) are beneficial for the storage, transport and use of polyethylene compositions because less volume is required for them and therefore, for example, in pelletizing operations, greater manufacturing throughput is possible given dimensioned equipment. equipment), such as an extruder or pelletizer.

Embodiments of the polyethylene compositions of the invention, such as the ethylene/alpha-olefin copolymer compositions of the invention, having a substantially uniform comonomer composition distribution are particularly advantageous in the manufacture of these films, so that the films thus produced can be substantially It is expected to have improved mechanical properties due to uniform comonomer composition distribution.

Justice .

Composition: It is a chemical composition. It is the arrangement, type, and ratio of atoms within a molecule, and the types and relative amounts of molecules within a component or substance.

Compound: A molecule or collection of molecules.

Concentration: A method of slowly increasing the mass or molar amount of less volatile chemical component(s) per unit volume of a continuous mixture containing more volatile chemical component(s) and less volatile chemical component(s). am. The method gradually removes more of the more volatile chemical component(s) than the less volatile component(s) from the continuous mixture, thereby producing a higher mass or molar amount of the less volatile chemical component(s) per unit volume than the continuous mixture. A concentrate having the component(s) is provided. The concentrate may be a precipitated solid.

Comonomer Composition Distribution or CCD: Change in weight percent (wt%) or mole percent (mol%) of the comonomer content of the ethylene/alpha-olefin copolymer composition on the y-axis versus the ethylene/alpha-olefin copolymer on the x-axis. This is a line plot of the change in LogM (by GPC) of the composition.

Substantially uniform comonomer composition distribution: comonomer content weight percent (wt%) or mole percent (mol%) of the ethylene/alpha-olefin copolymer composition on the y-axis versus the ethylene/alpha-olefin copolymer on the x-axis. A plot of the change in LogM (by GPC) of the composition has a flat (uniform CCD) or gently sloping upward or downward line (substantially uniform CCD). A perfectly flat line diagram has a slope or slope, m, equal to zero (m=0). Lines that become higher as they go from left to right have a slope m greater than zero. Lines that become lower as they go from left to right have a slope m less than zero. Ethylene/alpha-olefin copolymer compositions with substantially uniform CCDs are expected to have improved mechanical and/or optical properties over comparative ethylene/alpha-olefin copolymer compositions with normal or conventional CCDs.

Composition Distribution Breadth Index (CDBI). The CDBI value represents the weight percent of ethylene/alpha-olefin copolymer molecules with a comonomer content within 50% of the median total molar comonomer content. The relatively high CDBI values indicate that most copolymer molecules have a comonomer content within 50% of the median comonomer content, further indicating that the copolymer polymer is relatively homogeneous in comonomer content. The CDBI value of a linear polyethylene homopolymer containing no comonomer is defined to be 100%. Methods for calculating the CDBI value of copolymers are known in the art, for example from WO 93/03093. If the CDBI value for the first copolymer is higher than the CDBI value of the second copolymer, the higher CDBI value indicates that the comonomer distribution of the first copolymer is more controlled or limited than the comonomer distribution of the second copolymer. . The CDBI values of copolymers can be determined using techniques known in the art, such as, for example, US 5,008,204 or Wild et al., J. Poly. Sci. Polv. Phys. Ed., vol. 20, p. 441 (1982).

essentially consisting of, essentially consisting of, etc.: a partially closed final expression that excludes those that affect the basic and new features of the expression and allows others.

Consisting of, and consists of: A closed-ended expression that excludes what is not specifically stated by the modifying restriction. In some embodiments, any one or alternatively the expression “consisting essentially of” or “consisting essentially of” may be replaced with the expression “consisting of” or “consisting of” respectively.

(co)polymerize: polymerize a monomer, or copolymerize a monomer and at least one comonomer.

dWf/{dLog M (by GPC): GPC is gel permeation chromatography, dWf is the change in weight fraction, and dLogM is also referred to as dLog(MW) and is the change in logarithm of molecular weight.

dry. myriad. A moisture content of 0 to less than 5 ppm, based on total parts by weight. The material fed to the reactor(s) during the polymerization reaction is dry.

Effective amount: An amount sufficient to achieve the intended and appreciable beneficial result.

supplies. The amount of reactant and/or reagent added or “fed” to the reactor. In a continuous polymerization operation, each feed can independently be continuous or intermittent. Amounts or “feeds” can be measured by metering to control the amounts and relative amounts of the various reactants and reagents in the reactor at any given time.

Film: The claimed film properties are measured on a 25 micrometer thick single layer film.

Hydrophobic pretreated fumed silica: contacting untreated fumed silica with a hydrophobizing agent to react with surface hydroxyl groups on the untreated fumed silica, thereby modifying the surface chemistry of the fumed silica to provide hydrophobic pretreated fumed silica. It is a reaction product. The hydrophobizing agent may be silicone-based.

Untreated fumed silica: This is pyrogenic silica produced from a flame. It consists of amorphous silica powder prepared by fusing microscopic droplets into branched, chain-like, three-dimensional secondary particles, which agglomerate into tertiary particles. It's not quartz.

Hydrophobizing agent: An organic or organosilicon compound that forms a stable reaction product with the surface hydroxyl groups of fumed silica.

Induced Condensation Agent (ICA): An inert liquid useful for cooling materials in gas phase polymerization reactor(s) (e.g., fluidized bed reactors).

Inert: Generally, it is not (appreciably) reactive or does not interfere (appreciably) with the polymerization reaction of the present invention. The term "inert" as applied to a purge gas or ethylene feed means a molecular oxygen (O ₂ ) content of 0 to less than 5 ppm, based on the total weight of the purge gas or ethylene feed.

LogM is also referred to as Log(MW) and is a logarithmic function of molecular weight.

Mesoporous: Has an average pore diameter of 2 to 50 nanometers (nm).

Microporous: Having an average pore diameter of less than 2 nm.

Modifier: A composition that alters the reactivity, stability, or both of the components with which the composition acts.

Polyethylene: A macromolecule or collection of macromolecules consisting of constitutional units, wherein 50 to 100 mole percent (mol%), alternatively 70 to 100 mole%, alternatively 80 to 100 mole%, alternatively typically 90 to 100 mole percent, alternatively 95 to 100 mole percent, alternatively any one of the foregoing ranges of such units derived from ethylene monomer, with the upper endpoint being <100 mole percent; In embodiments where less than 100 mole percent of ethylene units are present, the remaining units are comonomeric units derived from at least one (C ₃ -C ₂₀ )alpha-olefin; It is a collection of these macromolecules.

(Pro)catalyst: A procatalyst, a catalyst, or a combination of a procatalyst and a catalyst.

Quartz: An untreated, non-porous crystalline form of silicon dioxide. Particulate or bulk.

Silica. It is a particulate form of silicon dioxide that may be amorphous. Crystalline, or gel-like. Includes fused silica, fumed silica, silica gel, and silica aerogel.

Spray-drying: Rapid drying of particulate solids containing less volatile chemical components through aspiration of a bulk mixture of less volatile and more volatile chemical components through a nebulizer using hot gases. It is to be formed. The particle size and shape of the particulate solid formed by spray-drying may be different from that of the precipitated solid.

System: An interrelated arrangement of different chemical components to form a functional whole.

Transportation: Movement from place to place. from reactor to reactor, from tank to reactor, from reactor to tank, and from manufacturing plant to storage facility, and vice versa.

Ziegler-Natta (pre-)catalyst and Ziegler-Natta (pre-)catalyst systems. Please refer to the contents of the invention. All these forms generally belong to the heterogeneous class of Ziegler-Natta (pro)catalysts and systems because they form the solid phase in gas-phase or liquid-phase olefin polymerization reactions.

matter.

Activator. Activators may include (C ₁ -C ₄ )alkyl-containing aluminum compounds. The (C ₁ -C ₄ )alkyl-containing aluminum compound is independently selected from 1, 2, or 3 (C ₁ -C ₄ )alkyl groups, and 2 alkyl groups each independently selected from chloride atoms and (C ₁ -C ₄ )alkoxides. , may contain 1 or 0 groups. Each C ₁ -C ₄ )alkyl is independently methyl; ethyl; profile; 1-methylethyl; butyl; 1-methylpropyl; 2-methylpropyl; Or it may be 1,1-dimethylethyl. Each (C ₁ -C ₄ )alkoxide is independently methoxide; ethoxide; propoxide; 1-methyl ethoxide; butoxide; 1-methylpropoxide; 2-methylpropoxide; Or it may be 1,1-dimethyl ethoxide. (C ₁ -C ₄ )Alkyl-containing aluminum compounds include triethylaluminum (TEA), triisobutyl aluminum (TIBA), diethylaluminum chloride (DEAC), diethylaluminum ethoxide (DEAE), and ethyl aluminum dichloride ( EADC), or a combination or mixture of any two or more of them. The activator may be triethylaluminum (TEA), triisobutylaluminum (TIBA), diethylaluminum chloride (DEAC), diethylaluminum ethoxide (DEAE) or ethyl aluminum dichloride (EADC).

(C ₃ -C ₂₀ )alpha-olefin. Compounds of formula (I): H ₂ C=C(H)-R (I), where R is a straight-chain (C ₁ -C ₁₈ )alkyl group. (C ₁ -C ₁₈ )alkyl groups are monovalent unsubstituted saturated hydrocarbons having 1 to 18 carbon atoms. Examples of R are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl. In some embodiments, the (C ₃ -C ₂₀ )alpha-olefin is 1-propene, 1-butene, 1-hexene or 1-octene; alternatively 1-butene, 1-hexene or 1-octene; alternatively 1-butene or 1-hexene; alternatively 1-butene or 1-octene; alternatively 1-hexene or 1-octene; Alternatively 1-butene; Alternatively 1-hexene; alternatively 1-octene; Alternatively, it is a combination of any two of 1-butene, 1-hexene, and 1-octene.

Carrier material. Before treatment with a hydrophobizing agent, the carrier material is untreated silica and has a variable surface area and average particle size. In some embodiments, the surface area is 50 to 150 square meters per gram (m ² /g). The average particle size may be less than 1 micrometer (μm). Each of the above properties is measured using conventional techniques known in the art. The untreated silica may be amorphous silica (not quartz), alternatively amorphous silica, alternatively fumed silica. Such silica is commercially available from numerous sources. Silica can be in the form of spherical particles, which are obtained by a spray-drying process. Untreated silica may be calcined (i.e., dehydrated) or uncalcined prior to treatment with a hydrophobizing agent.

Ethylene: It is a compound with the formula H ₂ C=CH ₂ .

Hydrophobizer, silicone-based: An organosilicon compound that forms suitable reaction products with the surface hydroxyl groups of fumed silica. The organosilicon compound may be a polydiorganosiloxane compound or an organosilicon monomer, which reacts with the surface hydroxyl groups of untreated fumed silica to form a Si-O-Si linkage with the loss of a water molecule as a by-product. Contains a bound leaving group (e.g. Si-halogen, Si-acetoxy, Si-oxymo (Si-ON=C<), Si-alkoxy or Si-amino group). Polydiorganosiloxane compounds, such as polydimethylsiloxane, contain backbone Si-O-Si groups, where oxygen atoms can form stable hydrogen bonds with the surface hydroxyl groups of fumed silica. Silicone-based hydrophobizing agents include trimethylsilyl chloride, dimethyldichlorosilane, polydimethylsiloxane fluid, hexamethyldisilazane, octyltrialkoxysilane (e.g., octyltrimethoxysilane), and any combination of two or more thereof. You can.

Induced condensation agent or ICA. In some embodiments, ICA is a (C ₅ -C ₂₀ )alkane, alternatively a (C ₁₁ -C ₂₀ )alkane, or (C ₅ -C ₁₀ )alkane. In some embodiments, ICA is a (C ₅ -C ₁₀ )alkane. In some embodiments, the (C ₅ -C ₁₀ )alkane is pentane, such as normal-pentane or isopentane; hexene; heptene; octene; nonen; deken; or a combination of any two or more of these. In some embodiments, ICA is isopentane (i.e., 2-methylbutane). The polymerization process of the invention using ICA may be referred to herein as inert condensation mode operation (ICMO). Concentration of a gas phase measured using gas chromatography by calibrating peak area percent versus mole percent (mol%) with a gas mixture standard of known concentration of the appropriate gas phase constituents. The concentration may be 1 to 10 mole %, alternatively 3 to 8 mole %. Use of ICA is optional. In some aspects, ICA is used, including some of the embodiments of the invention described later. For example, in one aspect of the manufacturing method, a mixture of ICA and catalyst may be fed into a polymerization reactor. In another version of the method, the use of ICA can be omitted and the mixed pre-formulated dry catalyst can be fed as is, devoid of ICA, into the polymerization reactor.

reducing agent. It is an effective substance for chemically reducing the complex of TiCl ₃ and MgCl ₂ (Ti ^red ). The reducing agent may be used in a chemically reducing effective amount that is effective in forming a chemical reduction product but may be insufficient in activating the reduced complex of TiCl ₃ and MgCl ₂ . The reducing agent may be a trialkylaluminum, such as trihexylaluminum, a dialkylaluminum halide, such as diethylaluminum chloride, or, typically, a combination of trialkylaluminum and dialkylaluminum halides, such as a combination of trihexylaluminum and diethylaluminum chloride. there is.

Spray-dried Ziegler-Natta (pre-)catalyst systems are common. Although each form of spray-dried Ziegler-Natta (pro)catalyst system can be catalytically active in olefin polymerization reactions, the activated form typically has much greater catalytic activity than the respective procatalyst and reduced forms. and polymer productivity. All conditions being equal, the catalytic activity and polymer productivity of this reaction can vary from embodiment to embodiment of an activated spray-dried Ziegler-Natta catalyst system. These modifications are within the control of those skilled in the art and may depend on the particular composition and configuration of the activated spray-dried Ziegler-Natta catalyst system. Relevant composition factors include the loading of Ti and Mg and the molar ratio of Mg to Ti (“mag-tie ratio”). Relevant compositional parameters include average primary particle size; primary particle size distribution; particle agglomeration; and particle or agglomerated shapes of Ziegler-Natta catalyst particles. The methods of preparing the carrier materials and catalyst systems described above further define these constituent factors.

Spray-dried Ziegler-Natta (pro)catalyst systems can generally, independently, be present in the form of a dry powder, or in the form of a suspension or slurry in a saturated and/or aromatic hydrocarbon solvent. Saturated and/or aromatic hydrocarbon solvents can aid handling of the (pro)catalyst system. The saturated and/or aromatic hydrocarbon solvent may be an alkane or alkyl-substituted benzene (toluene or xylene).

Spray-dried Ziegler-Natta (pre)catalyst systems can generally, independently, be produced, prepared, reacted, reduced, activated, transformed, handled, stored and transported under conditions suitable for the particular purpose. These conditions include reaction conditions, storage conditions, and transport conditions. These conditions are generally well known in the art. For example, spray-dried Ziegler-Natta (pre)catalyst systems can be independently prepared under an inert atmosphere, such as a gas consisting of anhydrous N ₂ , He, and/or Ar; and/or saturated and/or aromatic hydrocarbon solvents, such as those described herein. These conditions may include techniques well known for such systems, such as the Schlenk line technique.

Type of polymerization .

Activated spray-dried Ziegler-Natta catalyst systems can be used in gas or liquid phase olefin polymerization reactions to enhance the polymerization rate of monomer and/or comonomer(s). Liquid phase reactions include slurry phase and solution phase. In some embodiments, the olefin polymerization reaction is conducted in the gas phase, alternatively in the liquid phase, alternatively in the slurry phase, alternatively in the solution phase. Conditions for gas-phase and liquid-phase olefin polymerization reactions are generally well known. For illustration, gas phase olefin polymerization reaction conditions are described below.

Polymerization reactor .

Polymerization can be carried out in a high pressure, liquid phase or gas phase polymerization reactor to produce the polyethylene composition of the present invention. Such reactors and methods are generally known in the art. For example, the liquid phase polymerization reactor/process may be solution phase or slurry phase as described in US 3,324,095. Gas phase polymerization reactors/processes are described, for example, in US 4,453,399; US 4,588,790; US 4,994,534; US 5,352,749; US 5,462,999; and US 6,489,408, using stirred bed gas phase polymerization reactors (SB-GPP reactors) and fluidized bed gas phase polymerization reactors (FB-GPP reactors) and induction condensation agents and carried out in condensation mode polymerization. Gas phase polymerization reactors/processes are described in US 3,709,853; US 4,003,712; US 4,011,382; US 4,302,566; US 4,543,399; US 4,882,400; US 5,352,749; US 5,541,270; EP-A-0 802 No. 202; and the fluidized bed reactor/method described in Belgian Patent No. 839,380. These patents disclose gas-phase polymerization processes in which the polymerization medium is fluidized or mechanically agitated by a continuous flow of gaseous monomer and diluent. Other gas phase processes considered include US 5,627,242; US 5,665,818; US 5,677,375; EP-A-0 794 No. 200; EP-B1-0 649 992; EP-A-0 802 No. 202; and continuous or multi-stage polymerization processes as described in EP-B-634421.

In an alternative embodiment, the polymerization reaction is carried out in a reactor vessel containing a fluidized bed of a powder of ethylene/alpha-olefin copolymer, and a distribution plate disposed above the bottom head, defining a bottom gas inlet and having an expansion section, or an outlet from the fluidized bed. A pilot scale fluidized bed gas phase polymerization reactor (pilot reactor) is used including a cyclone system on the top of the reactor vessel to reduce the amount of resin fines that may be present. The expansion section defines the gas outlet. The pilot reactor continuously cycles gas from out of the gas outlet in the expansion section at the top of the reactor vessel to the surroundings, down to or into the bottom gas inlet of the pilot reactor and through the distribution plate and fluidized bed. It further includes a compressor blower of sufficient power to loop. The pilot reactor further includes a cooling system to remove heat of polymerization and maintain the fluidized bed at the target temperature. The composition of gases such as ethylene, alpha-olefins, hydrogen and oxygen fed into the pilot reactor is monitored by an in-line gas chromatograph in a cycle loop to maintain specific concentrations that can define and control polymer properties. . In some embodiments, the gases are cooled so that their temperature drops below their dew point, with the pilot reactor in condensation mode operation (CMO) or induced condensation mode operation (ICMO). In CMO, the liquid is downstream of the cooler and in the bottom head below the distribution plate. The activated spray-dried Ziegler-Natta catalyst system can be fed into the pilot reactor from a high pressure apparatus as a slurry or dry powder, the slurry being fed through a syringe pump and the dry powder being fed through a metering disk. The catalyst system typically enters the fluidized bed at the lower third of the bed height of the system. The pilot reactor further includes an isolation port (product discharge system) for discharging the powder of the ethylene/alpha-olefin copolymer from the reactor vessel in response to an increase in fluidized bed weight as the polymerization reaction progresses, and a method for weighing the fluidized bed. .

polymerization conditions

(co)polymerization conditions. Valid variables of any consequence or combinations of such variables, such as catalyst composition; amount of reactant; molar ratio of the two reactants; absence of interfering substances (eg H ₂ O and O ₂ ); or an effective and useful process parameter (e.g., feed rate or temperature), step or sequence in the copolymerization process of the present invention in the polymerization reactor(s) for providing the polyethylene composition of the present invention.

At least one, alternatively each (co)polymerization condition can be fixed (i.e. not varied) during the preparation of the polyethylene composition of the invention. These fixed (co)polymerization conditions may be referred to herein as steady state (co)polymerization conditions. Steady state (co)polymerization conditions are useful for continuously preparing embodiments of the polyethylene compositions of the invention with identical polymer properties.

Alternatively, at least one, alternatively two or more (co)polymerization conditions may be used to provide a transition ( transition) or to a second embodiment of the polyethylene composition of the invention having a second set of polymer properties, which can be varied within their defined operating parameters during production of the polyethylene composition of the invention. The first set and the second set are different and each fall within the limitations described herein for the polyethylene compositions of the present invention. For example, all other (co)polymerization conditions being the same, the higher molar ratio of (C ₃ -C ₂₀ )alpha-olefin comonomer/ethylene feed in the inventive copolymerization process results in the resulting product, inventive polyethylene. Produces a lower density of the composition. Transition from one set of (co)polymerization conditions to another is permitted within the meaning of “(co)polymerization conditions” since the operating parameters of both sets of (co)polymerization conditions are within the range defined herein. . A beneficial consequence of the foregoing transition is that any of the described property values for the polyethylene compositions of the present invention can be achieved by a person skilled in the art in light of the teachings herein.

(Co)polymerization conditions for gas or liquid phase reactors/processes may additionally include one or more additives such as chain transfer agents, accelerators or scavengers. Chain transfer agents are well known and can be alkyl metals such as diethyl zinc. Accelerators are well known from US 4,988,783 and may include chloroform, CFCl ₃ , trichloroethane and difluorotetrachloroethane. The remover may be trialkylaluminum. Slurry phase or gas phase polymerization can be operated in the absence of scavengers (not intentionally added). (Co)polymerization conditions for gas phase reactors/polymerizations additionally include amounts of continuity additives and/or static modifiers such as aluminum stearate or polyethyleneimine (e.g. 0.5 to 200 ppm based on all feeds in the reactor). can do. Static modifiers can be added to the gas phase reactor to inhibit the formation or accumulation of static charge therein.

(Co)polymerization conditions may further include the use of molecular hydrogen to control the final properties of the polyethylene composition. This use of H ₂ is generally described in the Propylene Handbook 76-78 (Hanser Publishers, 1996). All else being equal, the use of hydrogen can increase the melt flow rate (MFR) or melt index (MI); however, the MFR or MI is affected by the hydrogen concentration. The molar ratio of hydrogen to total monomer (H ₂ /monomer), hydrogen to ethylene (H ₂ /C ₂ ) or hydrogen to comonomer (H ₂ /α-olefin) is 0.0001 to 10, alternatively 0.0005 to 5, alternatively. It can be 0.001 to 3, alternatively 0.001 to 0.10.

(Co)polymerization conditions are independently 690 to 3450 kPa (kPa), 100 to 500 psia (pounds per square inch absolute), alternatively 1030 to 2070 kPa (150 psia) in the copolymerization reactor(s). to 300 psi), alternatively 1380 to 1720 kPa (200 to 250 psia), alternatively 1450 to 1590 kPa (210 to 230 psia), such as 1520 kPa (220 psia). 1.000 psia = 6.8948 kPa.

In some embodiments, the gas phase polymerization is performed in a fluidized bed-gas phase polymerization (FB-GPP) reactor under relevant gas-phase, fluidized bed polymerization conditions. These conditions are any variable or combination of variables that can affect the composition or properties of the polymerization reaction in the FB-GPP reactor or the ethylene/alpha-olefin copolymer product produced thereby. These variables include reactor design and size, catalyst composition and amount; reactant composition and amount; molar ratio of two different reactants; Presence or absence of feed gases such as H ₂ and/or O ₂ , molar ratio of feed gas to reactants, absence or concentration of interfering substances (e.g. H ₂ O), absence or presence of induced condensation agent (ICA), This may include the average polymer residence time in the reactor (avgPRT), partial pressures of the components, feed rates of monomers, reactor bed temperature (e.g., fluidized bed temperature), nature or sequence of process steps, and periods for transitions between steps. You can. In carrying out the method of the present invention, variables other than those described or varied by the method of the present invention may be held constant.

The comonomer/ethylene gas molar ratio Cx/C2 of the comonomer and ethylene fed to the FB-GPP reactor may be 0.0001 to 0.1, alternatively 0.0002 to 0.05, alternatively 0.0004 to 0.02.

Ethylene partial pressure in the FB-GPP reactor. 690 to 2070 kilopascals (kPa, i.e., 100 to 300 psia (pounds per square inch absolute)); alternatively 830 to 1655 kPa (120 to 240 psia), alternatively 1300 to 1515 kPa (190 to 220 psia). Alternatively, the partial pressure of ethylene is 690 to 3450 kilopascals (kPa, 100 to 500 psia). pounds per square inch absolute), alternatively 1030 to 2070 kPa (150 to 300 psia), alternatively 1380 to 1720 kPa (200 to 250 psia), alternatively 1450 to 1590 kPa (210 to 230 psia), For example, it may be 1520 kPa (220 psia). 1.000 psia = 6.8948 kPa.

The hydrogen to ethylene (H ₂ /C ₂ ) gas molar ratio in the FB-GPP reactor is 0.0001 to 0.25, alternatively 0.0005 to 0.200, alternatively 0.005 to 0.149, alternatively 0.009 to 0.109, alternatively 0.010 to 0.100. You can.

Oxygen (O ₂ ) concentration relative to ethylene in the FB-GPP reactor (“O ₂ /C ₂ “, parts by volume of O ₂ per million volume parts of ethylene (ppmv)). Typically, oxygen is not intentionally introduced into the FB-GPP reactor. In some embodiments, the FB-GPP reactor is substantially free or completely free of O ₂ , for example, O ₂ /C ₂ is between 0.0000 and 0.0001 ppmv, alternatively 0.0000 ppmv.

The reactor bed temperature in the FB-GPP reactor is 90°C to 120°C, alternatively 95°C to 115°C, alternatively 99°C to 110°C, alternatively 100.0°C to 109°C, alternatively 87.0°C to 89°C. It can be.

Average residence time for polymer (avgPRT). It is the average number of minutes or hours that the polymer product resides in the FB-GPP reactor. The avgPRT can be from 30 minutes to 10 hours, alternatively from 60 minutes to 5 hours, alternatively from 90 minutes to 4 hours, alternatively from 1.7 to 3.0 hours.

Startup or restart of gas phase reactors and polymerization methods

Start-up or restart of the retried FB-GPP reactor (cold start) or transition Restart of the FB-GPP reactor (warm start) includes the period before the steady-state polymerization conditions of step (a) are reached. Start-up or restart may involve the use of a polymer seedbed, pre-loaded or loaded, respectively, into the fluidized bed reactor. The polymer seedbed may consist of a powder of polyethylene, such as a polyethylene homopolymer or an ethylene/alpha-olefin copolymer.

Starting or restarting the FB-GPP reactor also involves removing air or other unwanted gas(es) from the reactor with a dry (dry) inert purge gas, followed by removing the dry inert purge gas from the FB-GPP reactor with dry ethylene gas. It may include a gas atmosphere transition including. The dry inert purge gas may consist essentially of molecular nitrogen (N ₂ ), argon, helium, or mixtures of any two or more of these. When not in operation, before start-up (cold start), the FB-GPP reactor contains the ambient atmosphere. The dry inert purge gas can be used to sweep air from the restarted FB-GPP reactor during the initial stages of startup to provide the FB-GPP reactor with an atmosphere comprised of a dry inert purge gas. Before restart (e.g., after a change in seedbed), the transition FB-GPP reactor may contain an atmosphere of unwanted ICA or other unwanted gases or vapors. The dry inert purge gas may be used to sweep away unwanted vapors or gases from the transition FB-GPP reactor during the initial stages of restart and provide an atmosphere consisting of a dry inert purge gas to the FB-GPP reactor. Any dry inert purge gas itself can be swept from the FB-GPP reactor as dry ethylene gas. The dry ethylene gas may further contain molecular hydrogen gas so that the dry ethylene gas is supplied to the fluidized bed reactor as a mixture thereof. Alternatively, dry molecular hydrogen gas can be introduced separately and after the atmosphere of the fluidized bed reactor has been converted to ethylene. The gas atmosphere transition can be performed before, during, or after heating the FB-GPP reactor to the reaction temperature of the polymerization conditions.

Starting or restarting the FB-GPP reactor also includes introducing feeds of reactants and reagents. Reactants include ethylene and alpha-olefin. Reagents fed into the fluidized bed reactor include molecular hydrogen gas and induced condensation agent (ICA) and an activated spray-dried Ziegler-Natta catalyst system.

The compound includes all isotopes thereof and naturally abundant and isotopically-enriched forms. The reinforced form may have medical or anti-counterfeiting applications.

In some embodiments, any compound, composition, agent, mixture or reaction product herein refers to H, Li, Be, B, C, N, O, F, Na, Mg, Al, Si, P, S, Cl, K , Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Br, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh , Pd, Ag, Cd, In, Sn, Sb, Te, I, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, lanthanides and actinium. Any one of the chemical elements selected from the group consisting of group elements may be absent, provided that the compound, composition, formulation, or reaction product (e.g., C and H required by polyolefins or C, H and O required by alcohols ) shall be subject to the condition that chemical elements required by ) are not excluded.

Catalyst productivity: Calculated as kilograms of (co)polymer resin produced per kilogram of catalyst used (“kg copolymer/kg catalyst” or simply “kg/kg”). Calculation of kilograms of catalyst used is based on the amount of titanium in the polymer as measured by X-ray fluorescence spectroscopy ("Ti IXRF") or by inductively coupled plasma optical emission spectroscopy ("Ti ICPES"). Catalyst productivity can be expressed as a range from kg/kg (as determined by Ti IXRF) to kg/kg (as determined by Ti ICPES).

Transparency Test Method: ASTM D1746-15, Standard Test Method for Transparency of Plastic Sheeting . Results are expressed as percent transmittance (%).

Falling Dart Test Method: Measured according to Method A , Standard Test Methods for Impact Resistance of Plastic Film by the Free-Falling Dart Test Method in ASTM D1709-16a. Method A uses a falling weight with a hemispherical head with a diameter of 38.10 ± 0.13 mm (1.500 ± 0.005 inches) that is dropped from a height of 0.66 ± 0.01 m (26.0 ± 0.4 inches). This test method can be used for films with impact resistance that would require a mass of less than about 50 g to about 6 kg to rupture the film. The results were expressed in grams (g).

Density Test Method: According to ASTM D792-13, Standard Test Methods for Density and Specific Gravity (Relative Density) of Plastics by Displacement, Method B (Testing of solid plastics in liquids other than water, e.g., 2-propanol liquid). It is measured. Report results in grams per cubic centimeter (g/cm ³ ).

Elmendorf Tear Test Method: Measured in accordance with ASTM D1922-09, Standard Test Methods for Propagation Tear Resistance of Plastic Film and Thin Sheeting by Pendulum Method, Type B (constant radius). Report results as normalized tear in the cross direction (CD) or machine direction (MD) in gram-force (gf) (technically equivalent to ISO 6383-2).

Film Puncture Test Method: ASTM D5748 - 95 (2012), Standard Test Method for Protrusion Puncture Resistance of Stretch Wrap Film . Determine the puncture resistance of the film as its resistance to penetration by a probe impinging the film at a standard speed, 250 millimeters per minute (mm/min). The probe is coated with polytetrafluoroethylene and has an outer diameter of 1.905 cm (0.75 inches). The film is clamped during testing. The probe eventually penetrates or cuts the clamped film. The peak force at break, i.e. the maximum force, energy (work), to cut or penetrate the clamped film, and the distance the probe penetrates at break are recorded using mechanical testing software. The probe imposes a biaxial stress on the clamped film, which represents the type of stress the film encounters in many product end uses. This resistance is a measure of the energy-absorbing ability of the film to resist puncture under these conditions. The results are expressed as foot-pound force per cubic inch (ft*Ibf/in ³ ).

Flow index (190℃, 21.6 kg, "FI ₂₁ ") Test method: ASTM D1238-13, Standard Test Method for Melt Flow Rates of Thermoplastics by Extrusion Platometer using the conditions of 190℃/21.6 kilogram (kg) . Report results in grams eluted per 10 minutes (g/10 minutes) or equivalent decigrams per minute (dg/1 minute).

Flow Rate (190°C, 5.0 kilograms (kg), "I ₅ ") Test Method: Ethylene-based in accordance with ASTM D1238-13 using the conditions of 190°C/5.0 kg (previously referred to as "Condition E" and also referred to as I ₅ ). Measurements are made on (co)polymers. Report results in grams eluted per 10 minutes (g/10 minutes) or equivalent decigrams per minute (dg/1 minute).

Flow rate ratio (190℃, "I ₂₁ /I ₅ ") Test method: Calculated by dividing the value of the flow index I ₂₁ test method by the value of the flow rate I ₅ test method. No units.

Fluidized Bulk Density (FBD) Test Method: Defined as the weight of solids per unit volume of the fluidized bed at a given critical gas velocity (SGV). FBD (uncorrected) = (ΔP * S)/(S1*H), where ΔP is the pressure drop between the bottom and middle tabs, in pounds per square inch (lb/in). ² or psi), S represents the cross-sectional area of the reactor in square inches (in ² ), S1 represents the cross-sectional area of the reactor in square feet (ft ² ), and H represents the distance between the bottom and middle tabs, in feet ( ft). FBD (uncalibrated) is calibrated to actual values based on reactor pressure and temperature and gas density (FDC (calibrated)). The unit of FBD (correction) can be converted to kilogram per cubic meter (kg/m ³ ).

Gel permeation chromatography (GPC) method: Weight-average molecular weight Test method: M _w , number average molecular weight (M _n ), and M _w /M using chromatograms obtained on a high-temperature gel permeation chromatography instrument (HTGPC, Polymer Laboratories). Determine _n . The HTGPC is equipped with a transfer line, differential refractive index detector (DRI), and three Polymer Laboratories PLgel 10 μm Mixed-B columns, all housed in an oven maintained at 160°C. The method uses a solvent consisting of BHT-treated TCB at a nominal flow rate of 1.0 milliliters per minute (mL/min) and a nominal injection volume of 300 microliters (μL). To provide a solvent, dissolve 6 g of butylated hydroxytoluene (BHT, an antioxidant) in 4 liters (L) of reagent grade 1,2,4-trichlorobenzene (TCB) and 0.1 micrometer (μm) Teflon. A solvent is prepared by filtering the obtained solution through a (Teflon) filter. The solvent is degassed with an in-line degassing device before entering the HTGPC equipment. The column is calibrated with a series of monodisperse polystyrene (PS) standards. Separately, a known amount of polymer in a known volume of solvent is heated with continuous shaking at 160° C. for 2 hours to prepare a test polymer of a known concentration dissolved in the solvent to provide a solution. (Measure all quantities gravimetrically.) Target solution concentration of the test polymer, c , from 0.5 to 2.0 milligrams of polymer per milliliter solution (mg/mL), as used for high molecular weight polymers, c . Before running each sample, purge the DRI detector. Then increase the flow rate of the device to 1.0 mL/min/ and allow the DRI detector to stabilize for 8 h before injecting the first sample. Calculate M _w and M _n using the column correction and the universal correction relationship. Calculate MW at each dissolution volume using the following equation: , the subscript “X” indicates the test sample, the subscript “PS” indicates the PS standard, , , and and is obtained from published literature. For polyethylene, a _x /K _x = 0.695/0.000579. For polypropylene a _x /K _x = 0.705/0.0002288. At each time point in the generated chromatogram, calculate the concentration c from the baseline subtracted DRI signal, I _DRI , using the following formula: c = K _DRI I _DRI /(dn/dc), where K _DRI is DRI is a constant determined by correction, / represents division, and dn/dc is the refractive index increment for the polymer. For polyethylene, dn/dc = 0.109. Calculate the mass recovery of the polymer from the ratio of the injection mass equal to the predetermined concentration multiplied by the integrated area of the chromatogram of the concentration chromatograph and the injection loop volume to the elution volume. Unless otherwise indicated, all molecular weights are reported in grams per mole (g/mole). Further details regarding methods for determining Mw, Mn, MWD are described in US 2006/0173123, pages 24-25, paragraphs [0334] to [0341]. A plot of log(MW) on the x-axis versus dW/dLog(MW) on the y-axis to provide a GPC chromatogram, where log(MW) and dW/dLog(MW) are as defined above.

Melt Flow Ratio (190°C, "I ₂₁ /I ₂ ") Test Method: Calculated by dividing the value from the Flow Index I ₂₁ test method by the value from the Melt Index I ₂ test method. No units.

Melt Index (190°C, 2.16 kilograms (kg), "I ₂ ") Test Method: Condition 190°C/2.16 kg, formerly known as "Condition E" and also known as I ₂ for ethylene-based (co)polymers. Measured according to ASTM D1238-13 using . Report results in grams eluted per 10 minutes (g/10 minutes) or equivalent decigrams per minute (dg/1 minute). 10.0 dg = 1.00 g. The melt index is inversely proportional to the weight average molecular weight of the polyethylene, although it is not linear. Therefore, the higher the molecular weight, the lower the melt index.

Optical Gloss Test Method: ASTM D2457-13, Standard Test Method for Specular Gloss of Plastic Films and Solid Plastics . Specular gloss is measured using a glassometer at angles of incidence of 20°, 45°, 60° or 75°. The gloss of a mirror surface has no units.

Optical Haze Test Method: ASTM D1003-13, Standard Test Method for Haze and Luminous Transmittance of Transparent Plastics . Haze is measured using a hazemeter. Haze is expressed as the percentage of luminous transmission that deviates from the incident light due to forward scattering as it passes through the film. Results are expressed as percentages (%).

1% or 2% Secant Modulus Test Method: Measured according to ASTM D882-12, Standard Test Methods for Tensile Properties of Thin Plastic Sheeting . Use a secant factor of 1% or 2% in the transverse direction (CD) or machine direction (MD). Results are reported in megapascals (MPa). 1,000.0 pounds per square inch (psi) = 6.8948 MPa.

Sedimented Bulk Density (SBD) Test Method: Defined as the weight of material per unit volume. SBD is measured by pouring the amount of polymer resin to overflow into a tared 400 cubic centimeter (cm ³ ) volume cylinder under gravity, after removing excess polymer resin by sliding a straight edge across the top of the cylinder, resulting in Weigh the cylinder level full, subtract the tare weight of the cylinder, and divide the resulting resin weight by the cylinder volume to obtain SBD in pounds per cubic foot ( ^pounds per cubic foot). It can be converted to lb/ft ³ ) or kilograms per cubic meter (kg/m ³ ).

Tensile modulus test method: Measured according to ASTM D882-12, Standard Test Methods for Tensile Properties of Thin Plastic Sheeting . Reported results are either transverse direction (CD) as yield average strain in percent (%) or yield average stress in megapascals (MPa), or machine direction (MD) as yield average strain in percent (%). . 1,000.0 pounds per square inch (psi) = 6.8948 MPa.

Diethylaluminum chloride: Obtained from Albemarle Corporation.

Magnesium dichloride: support material; Obtained from SRC Worldwide Inc.

Magnesium metal chips (Grignard chips): Aldrich Chemical.

Hydrophobic fumed silica 1: carrier material; It is a low surface area fumed silica activated with dimethyldichlorosilane available from Cabot Corporation as TS-610.

Tetrahydrofuran, Anhydrous: Organic modifier; Obtained from Pride Chemical Solutions.

Titanium tetrachloride: Obtained from WR Grace.

Titanium trichloride.AA: Obtained from WR Grace.

Triethylaluminum: activator; Obtained from Albermarle or Akzo.

Trihexyl Aluminum: Reducing agent; Obtained from Albermarle or Akzo. Also known as tri-n-hexyl aluminum or TnHal.

1-Butene (“C4”): comonomer; In Tables 1 and 2, it is used as the molar ratio of C4/C2.

Ethylene (“C2”): monomer; It is used as the partial pressure of C2 in Tables 1 and 2.

Isopentane: Induced Condensing Agent 1 (“ICA1”); In Tables 1 and 2, mole percent (mol%) concentrations are used in the gas phase of the gas phase reactor relative to the total molar content of the gas phase matter.

Molecular hydrogen gas (“H2”): In Tables 1 and 2, the molar ratio H2/C2 is used.

Formulation 1: Synthesis of a modified spray-dried Ziegler-Natta procatalyst system modified by tetrahydrofuran. Anhydrous tetrahydrofuran (28 kg) is added to the feed tank. Next, TiCl ₄ (530 grams (g)) and Mg metal (36 g) are added. The resulting solution is heated to 60° C. and the solution is mixed for 1 hour to form a first solution. Afterwards, finely divided solid MgCl ₂ (1340 g) is added and mixed at 60° C. for 5 hours or overnight to dissolve the MgCl ₂ and prepare a second solution. Once MgCl ₂ is dissolved, the second solution is cooled to 40°C to 45°C. Afterwards, hydrophobic pretreated fumed silica (Cabosil TS-610, 1.7 kg) is added to provide a suspension. The suspension is mixed for 30 minutes to provide a slurry of the modified Ziegler-Natta procatalyst system and hydrophobic pretreated fumed silica. The slurry is sprayed into a spray dryer under the following conditions: inlet temperature 160°C, outlet temperature 110°C, feed rate approximately 45 kg/hour, total gas flow rate approximately 270 kg/hour, atomizer speed: Formulation Typically varied to approximately 85% to provide a modified spray-dried Ziegler-Natta procatalyst system of 1.

Formulation 1a (prophetic): Synthesis of modified spray-dried Ziegler-Natta procatalyst, modified by tetrahydrofuran. Anhydrous tetrahydrofuran (28 kg) is added to the feed tank. Next, finely divided solid MgCl ₂ (1255 g) is added. Heat the mixture to 60° C. and mix the mixture for 5 hours or overnight to form the third solution. The third solution is cooled to 40°C to 45°C. Afterwards, TiCl ₃ .AA (459 g) is added and mixed for 1 hour. Afterwards, hydrophobic pretreated fumed silica (Cabosil TS-610, 1.6 kg) is added to provide a suspension. The suspension is mixed for 30 minutes to provide a slurry of the modified Ziegler-Natta procatalyst system and hydrophobic pretreated fumed silica. The slurry was sprayed into a spray dryer using the spray-drying conditions of Formulation 1 to provide the modified spray-dried Ziegler-Natta procatalyst system of Formulation 1a.

Formulation 2 (actual) or 2a (propetic): Synthesis of reduced spray-dried Ziegler-Natta catalyst system modified by tetrahydrofuran. The modified spray-dried Ziegler-Natta procatalyst system prepared by the scaled-up version of Formulation 1 (actual) or 1a (prophetic) was reacted with a chemically reducible effective amount in a 4 liter (L) volume mix tank. After contacting with a reagent mixture of 40 wt% trihexyl aluminum (TnHAl) reducing agent in mineral oil for approximately 1 hour to provide a reaction mixture, a reagent mixture of 12 wt% diethylaluminum chloride (DEAC) in mineral oil was added to the reaction mixture. Added to the mixture and mixed for an additional hour to provide the reduced spray-dried Ziegler-Natta catalyst system of Formulation 2 or 2a, respectively. The molar ratio of TnHAl to DEAC is approximately 0.875/1.000.

Inventive Example 1 (IE1, practical) or 1a (IE1a, propagate): Synthesis of activated spray-dried Ziegler-Natta catalyst system modified by tetrahydrofuran. The reduced spray-dried Ziegler-Natta catalyst system of Formulation 2 (actual) or 2a (propetic) was quenched at 25:75 of diethylaluminum chloride (DEAC) and triethylaluminum (TEAl or TEAL) activator in mineral oil. (wt/wt) contacting the mixture and co-feeding into the reactor by co-feeding into a bed or into a cycle gas line, an activated spray-dried Ziegler-Natta catalyst system of IE1 or 1a. are provided respectively.

Inventive Examples 2 (IE2, practical) and 2a (IE2a, prophetic): Same as IE1 or IE1a, respectively, except that the DEAC/TEAl weight/weight ratio is 60:40.

Comparative Example 1 (CE1): The procedure of IE1 is repeated, except that an activator consisting of TEAl is used instead of the activator mixture, providing an activated spray-dried Ziegler-Natta catalyst system of CE1. TEAl is fed into the reactor by feeding it to the bed or into the cycle gas line.

Inventive Example A (IE(A)): An ethylene/1-butene copolymer composition is provided by copolymerization of ethylene and 1-butene catalyzed by an activated spray-dried Ziegler-Natta catalyst system. Formulation 2 is fed into the reactor as a mineral oil slurry. Formulation 2 is fed into the reactor through a first feed line, and a DEAC/TEAl mixture at a weight/weight ratio of 25/75 is fed into the polymerization reactor through a second feed line, said first and second feed lines. is different. The ethylene/1-butene copolymer composition of IE(A) was produced in a single gas phase polymerization reactor with a capacity to produce 15 to 25 kg resin per hour. To conduct the experiment, a seedbed of granular resin was preloaded into the reactor before start-up. The reactor along with the seedbed was dried to less than 5 ppm moisture using high-purity nitrogen. The reaction component gases, ethylene, hydrogen and 1-butene, were then introduced into the reactor to build the desired gaseous composition as shown below in Table 1. At the same time, the reactor was heated to the desired temperature. Once (co)polymerization conditions are reached, a slurry feed of 17% by weight of Formulation 2 in mineral oil of the reduced spray-dried Ziegler-Natta catalyst system (modified with tetrahydrofuran) is fed to the first feed line. It was injected into the reactor through . At the same time, the DEAC/TEAl mixture at a weight/weight ratio of 27/75 was supplied into the polymerization reactor through a second supply line, and the first and second supply lines are different. Steady-state production of the ethylene/1-butene copolymer composition was reached using about 5 to 10 bed turnovers, thereby providing an embodiment of the inventive ethylene/1-butene copolymer composition of IE(A). . The ethylene/1-butene copolymer composition of the present invention was collected from the product discharge outlet of the reactor.

Inventive Example B (IE(B)): Same as IE(A) except that Formulation 2 is fed into the reactor as a mineral oil slurry. Formulation 2 is fed into the reactor through a first feed line, and a DEAC/TEAl mixture at a weight/weight ratio of 60/40 is fed into the polymerization reactor through a second feed line, said first and second feed lines. is different.

Comparative Example A (CE(A)): Copolymerization of ethylene and 1-butene catalyzed by the comparative activated spray-dried Ziegler-Natta catalyst system of CE1 to provide an ethylene/1-butene copolymer composition. Example A of the invention is repeated except that TEAl is used as the activator rather than DEAC. Reactor and process conditions are listed later in Table 2. A comparative ethylene/1-butene copolymer composition was collected from the product discharge outlet of the reactor.

Comparison of the inventive ethylene/1-butene copolymer compositions of IE(A) and IE(B) with CE(A). The ethylene/1-butene copolymer compositions were tested for MD- By stress @ yield, CD-stress @ yield, Elmendorf MD tear, Elmendorf CD tear, 2% MD secant factor, 2% CD secant factor, film penetration, dart impact, gloss (45°), clarity, and optical haze. It can be characterized. Comparative properties of the characterization of CE(A) can be normalized relative to the same by reporting them as 100. The inventive properties of the characterization of IE(A) and IE(B) can be independently determined from the characterization of CE(A) by dividing the inventive property values by the corresponding comparative property values and multiplying the result by 100. It can be normalized relative to the corresponding comparison feature. MD-stress @ yield, CD-stress @ yield, Elmendorf MD tear, Elmendorf CD tear, 2% MD secant factor, 2% CD secant factor, film puncture rate, dart impact, gloss (45°) and clarity, 100 A larger normalized value is an improvement over 100. For optical haze, a normalized value less than 100 is an improvement over 100.

As shown in the data in Tables 1 and 2, the inventive activated spray-dried Ziegler-Natta catalyst systems of IE1 and IE2 were prepared for the ethylene/alpha-olefin copolymer compositions of IE(A) and IE(B), respectively. These compositions unexpectedly yielded higher fluxes than the corresponding bulk densities of the comparative ethylene/alpha-olefin copolymer compositions of CE(A) produced with the comparative activated spray-dried Ziegler-Natta catalyst system of CE1. It had a higher bulk density and a higher settled bulk density.

As shown in the data in Table 3 or Figure 1, the inventive ethylene/1-butene copolymer of IE(A), and the associated inventive activated spray-dried Ziegler-Natta catalyst system of IE1, contain a comonomer Significant improvement was observed in composition distribution (CCD).

Claims (8)

An activated spray-dried Ziegler-Natta catalyst system comprising (A*) an activated Ziegler-Natta catalyst comprising an activated complex of TiCl ₃ and MgCl ₂ , (B) hydrophobic pretreated fumed silica, and an effective amount of (C ) an activator mixture of triethylaluminum (TEAl) and diethylaluminum chloride (DEAC) in a TEAl/DEAC weight/weight ratio of 25:75 to 75:25; or an activated spray-dried Ziegler-Natta catalyst system comprising their activation reaction products. delete A method of preparing the activated spray-dried Ziegler-Natta catalyst system of claim 1, wherein the method comprises a reduced Ziegler-Natta catalyst system comprising a chemical reduction product of a complex of (A ^red ) TiCl ₃ and MgCl ₂ . An activated spray-dried Ziegler-Natta catalyst system is prepared by contacting the reduced spray-dried Ziegler-Natta catalyst system comprising the Natta catalyst and (B) hydrophobic pretreated fumed silica with an effective amount of the activator mixture (C). A method comprising the step of manufacturing. A method of making a polyethylene composition comprising ethylene (monomer) and optionally 0, 1 or more (C ₃ -C ₂₀ )alpha-olefins (comonomer(s)) by the activated spray-drying process of claim 1. By contacting with a Ziegler-Natta catalyst system, polyethylene comprising a polyethylene homopolymer or an ethylene/(C ₃ -C ₂₀ )alpha-olefin copolymer, respectively, and an activated spray-dried Ziegler-Natta catalyst system, or by-products thereof. A method comprising providing a composition. 5. The polyethylene composition according to claim 4, by gas phase polymerization in one, two or more gas phase polymerization reactors under (co)polymerization conditions in the presence of molecular hydrogen gas (H ₂ ) and optionally an induced condensation agent (ICA). It includes manufacturing steps; The (co)polymerization conditions include a reaction temperature of 80°C to 110°C; molar ratio of molecular hydrogen gas to ethylene from 0.001 to 0.050; and a molar ratio of comonomer to ethylene of 0.005 to 0.10. ◈Claim 6 was abandoned upon payment of the setup registration fee.◈ 5. The method of claim 4, wherein ethylene and one or more (C ₃ -C ₂₀ )alpha-olefins (comonomer(s)) are copolymerized to provide an ethylene/(C ₃ -C ₂₀ )alpha-olefin copolymer composition. Method, including. A polyethylene composition produced by the method of claim 4. ◈Claim 8 was abandoned upon payment of the setup registration fee.◈ An article of manufacture comprising a shaped form of the polyethylene composition of claim 7.